Metal Complexes Containing Cyclopentadienyl Ligands

ABSTRACT

Metal complexes including cyclopentadienyl ligands and methods of using such metal complexes to prepare metal-containing films are provided.

FIELD OF THE INVENTION

The present technology relates generally to metal complexes includingcyclopentadienyl ligands, methods of preparing such complexes andmethods of preparing metal-containing thin films using such complexes.

BACKGROUND

Various precursors are used to form thin films and a variety ofdeposition techniques have been employed. Such techniques includereactive sputtering, ion-assisted deposition, sol-gel deposition,chemical vapor deposition (CVD) (also known as metalorganic CVD orMOCVD), and atomic layer deposition (ALD) (also known as atomic layerepitaxy). CVD and ALD processes are increasingly used as they have theadvantages of enhanced compositional control, high film uniformity, andeffective control of doping. Moreover, CVD and ALD processes provideexcellent conformal step coverage on highly non-planar geometriesassociated with modern microelectronic devices.

CVD is a chemical process whereby precursors are used to form a thinfilm on a substrate surface. In a typical CVD process, the precursorsare passed over the surface of a substrate (e.g., a wafer) in a lowpressure or ambient pressure reaction chamber. The precursors reactand/or decompose on the substrate surface creating a thin film ofdeposited material. Volatile by-products are removed by gas flow throughthe reaction chamber. The deposited film thickness can be difficult tocontrol because it depends on coordination of many parameters such astemperature, pressure, gas flow volumes and uniformity, chemicaldepletion effects, and time.

ALD is also a method for the deposition of thin films. It is aself-limiting, sequential, unique film growth technique based on surfacereactions that can provide precise thickness control and depositconformal thin films of materials provided by precursors onto surfacessubstrates of varying compositions. In ALD, the precursors are separatedduring the reaction. The first precursor is passed over the substratesurface producing a monolayer on the substrate surface. Any excessunreacted precursor is pumped out of the reaction chamber. A secondprecursor is then passed over the substrate surface and reacts with thefirst precursor, forming a second monolayer of film over thefirst-formed monolayer of film on the substrate surface. This cycle isrepeated to create a film of desired thickness.

Thin films, and in particular thin metal-containing films, have avariety of important applications, such as in nanotechnology and thefabrication of semiconductor devices. Examples of such applicationsinclude high-refractive index optical coatings, corrosion-protectioncoatings, photocatalytic self-cleaning glass coatings, biocompatiblecoatings, dielectric capacitor layers and gate dielectric insulatingfilms in field-effect transistors (FETs), capacitor electrodes, gateelectrodes, adhesive diffusion barriers, and integrated circuits.Dielectric thin films are also used in microelectronics applications,such as the high-κ dielectric oxide for dynamic random access memory(DRAM) applications and the ferroelectric perovskites used in infrareddetectors and non-volatile ferroelectric random access memories(NV-FeRAMs). The continual decrease in the size of microelectroniccomponents has increased the need for improved thin film technologies.

Technologies relating to the preparation of scandium-containing andyttrium-containing thin films (e.g., scandium oxide, yttrium oxide,etc.) are of particular interest. For example, scandium-containing filmshave found numerous practical applications in areas such as catalysts,batteries, memory devices, displays, sensors, and nano- andmicroelectronics and semiconductor devices. In the case of electronicapplications, commercial viable deposition methods usingscandium-containing and yttrium-containing precursors having suitableproperties including volatility, low melting point, reactivity andstability are needed. However, there are a limited number of availablescandium-containing and yttrium-containing compounds which possess suchsuitable properties. Accordingly, there exists significant interest inthe development of scandium and yttrium complexes with performancecharacteristics which make them suitable for use as precursor materialsin vapor deposition processes to prepare scandium-containing andyttrium-containing films. For example, scandium-containing andyttrium-containing precursors with improved performance characteristics(e.g., thermal stabilities, vapor pressures, and deposition rates) areneeded, as are methods of depositing thin films from such precursors.

SUMMARY

According to one aspect, a metal complex of Formula I is provided:[(R¹)_(n)Cp]₂M¹L¹ (I), wherein M¹ is a Group 3 metal or a lanthanide(e.g., scandium, yttrium and lanthanum); each R¹ is independentlyhydrogen, C₁-C₅-alkyl or silyl; n is 1, 2, 3, 4, or 5; Cp iscyclopentadienyl ring; and L¹ is selected from the group consisting of:NR²R³; N(SiR⁴R⁵R⁶)₂; 3,5-R⁷R⁸—C₃HN₂; 1-(R³²)C₃H₄; 1-R³³-3-R³⁴—C₃H₃; andR³⁵, R³⁶—C₃HO₂; wherein R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are eachindependently hydrogen or C₁-C₅-alkyl; and R³², R³³, R³⁴, R³⁵, and R³⁶are each independently alkyl or silyl; wherein when M¹ is yttrium and L¹is 3,5-R⁷R⁸—C₃HN₂, R¹ is C₁-C₅-alkyl or silyl; and wherein when M¹ isyttrium and L¹ is N(SiR⁴R⁵R⁶)₂, n is 1, 2, 3, or 4.

In other aspects, a metal complex of Formula II is provided:[((R⁹)_(n)Cp)₂M²L²]₂ (II), wherein M² is a Group 3 metal or a lanthanide(e.g., scandium, yttrium and lanthanum); each R⁹ is independentlyhydrogen or C₁-C₅-alkyl; n is 1, 2, 3, 4 or 5; Cp is cyclopentadienylring; and L² is selected from the group consisting of: Cl, F, Br, I, and3,5-R¹⁰R¹¹—C₃HN₂; wherein R¹⁰ and R¹¹ are each independently hydrogen orC₁-C₅-alkyl; wherein when M² is scandium and L² is Cl, R⁹ isC₁-C₅-alkyl.

In other aspects, methods of forming metal-containing films by vapordeposition, such as CVD and ALD, are provided herein. The methodcomprises vaporizing at least one metal complex corresponding instructure to Formula I: (R¹Cp)₂M¹L¹ (I), wherein M¹ is a Group 3 metalor a lanthanide (e.g., scandium, yttrium and lanthanum); each R¹ isindependently hydrogen, C₁-C₅-alkyl or silyl; Cp is cyclopentadienylring; and L¹ is selected from the group consisting of: NR²R³;N(SiR—⁴R⁵R⁶)₂; 3,5-R⁷R⁸—C₃HN₂; 1-(R³²)C₃H₄; 1-R³³-3-R³⁴—C₃H₃; and R³⁵,R³⁶—C₃HO₂; wherein R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are each independentlyhydrogen or C₁-C₅-alkyl; and R³², R³³, R³⁴, R³⁵, and R³⁶ are eachindependently alkyl or silyl.

Other embodiments, including particular aspects of the embodimentssummarized above, will be evident from the detailed description thatfollows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates XPS (X-ray Photoelectron Spectroscopy) analysis ofSc₂O₃ films using Sc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 2 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 3 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 4 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate.

FIG. 5 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 6 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 7 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 8 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 9 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 10 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 11 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 12 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 13 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 14 illustrates XPS analysis of Sc₂O₃ films usingSc(MeCp)₂(3,5-dimethyl-pyrazolate).

FIG. 15 illustrates dependence of ALD Y₂O₃ growth rate per cycle on thedeposition temperature when depositing [Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂.

FIG. 16 illustrates dependence of ALD Y₂O₃ growth rate per cycle on H₂Opurge time when depositing [Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂ at 125° C., 150°C. and 200° C.

FIG. 17 illustrates ALD Y₂O₃ growth rate per cycle at 3 differentpositions in a cross-flow reactor along the precursor/carrier gas flowdirection, the precursor inlet, the reactor center, and precursoroutlet.

DETAILED DESCRIPTION

Before describing several exemplary embodiments of the presenttechnology, it is to be understood that the technology is not limited tothe details of construction or process steps set forth in the followingdescription. The present technology is capable of other embodiments andof being practiced or being carried out in various ways. It is also tobe understood that the metal complexes and other chemical compounds maybe illustrated herein using structural formulas which have a particularstereochemistry. These illustrations are intended as examples only andare not to be construed as limiting the disclosed structure to anyparticular stereochemistry. Rather, the illustrated structures areintended to encompass all such metal complexes and chemical compoundshaving the indicated chemical formula.

In various aspects, metal complexes, methods of making such metalcomplexes, and methods of using such metal complexes to form thinmetal-containing films via vapor deposition processes, are provided.

As used herein, the terms “metal complex” (or more simply, “complex”)and “precursor” are used interchangeably and refer to metal-containingmolecule or compound which can be used to prepare a metal-containingfilm by a vapor deposition process such as, for example, ALD or CVD. Themetal complex may be deposited on, adsorbed to, decomposed on, deliveredto, and/or passed over a substrate or surface thereof, as to form ametal-containing film. In one or more embodiments, the metal complexesdisclosed herein are nickel complexes.

As used herein, the term “metal-containing film” includes not only anelemental metal film as more fully defined below, but also a film whichincludes a metal along with one or more elements, for example a metaloxide film, metal nitride film, metal silicide film, and the like. Asused herein, the terms “elemental metal film” and “pure metal film” areused interchangeably and refer to a film which consists of, or consistsessentially of, pure metal. For example, the elemental metal film mayinclude 100% pure metal or the elemental metal film may include at leastabout 90%, at least about 95%, at least about 96%, at least about 97%,at least about 98%, at least about 99%, at least about 99.9%, or atleast about 99.99% pure metal along with one or more impurities. Unlesscontext dictates otherwise, the term “metal film” shall be interpretedto mean an elemental metal film. In some embodiments, themetal-containing film is an elemental scandium or yttrium film. In otherembodiments, the metal-containing film is scandium oxide, yttrium oxide,scandium nitride, yttrium nitride, scandium silicide or yttrium silicidefilm. Such scandium-containing and yttrium-containing films may beprepared from various scandium and yttrium complexes described herein.

As used herein, the term “vapor deposition process” is used to refer toany type of vapor deposition technique, including but not limited to,CVD and ALD. In various embodiments, CVD may take the form ofconventional (i.e., continuous flow) CVD, liquid injection CVD, orphoto-assisted CVD. CVD may also take the form of a pulsed technique,i.e., pulsed CVD. In other embodiments, ALD may take the form ofconventional (i.e., pulsed injection) ALD, liquid injection ALD,photo-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. Theterm “vapor deposition process” further includes various vapordeposition techniques described in Chemical Vapour Deposition:Precursors, Processes, and Applications; Jones, A. C.; Hitchman, M. L.,Eds. The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp1-36.

The term “alkyl” (alone or in combination with another term(s)) refersto a saturated hydrocarbon chain of 1 to about 12 carbon atoms inlength, such as, but not limited to, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, decyl, and so forth. The alkyl group maybe straight-chain or branched-chain. “Alkyl” is intended to embrace allstructural isomeric forms of an alkyl group. For example, as usedherein, propyl encompasses both n-propyl and isopropyl; butylencompasses n-butyl, sec-butyl, isobutyl and tert-butyl; pentylencompasses n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl and3-pentyl. Further, as used herein, “Me” refers to methyl, “Et” refers toethyl, “Pr” refers to propyl, “i-Pr” refers to isopropyl, “Bu” refers tobutyl, “t-Bu” refers to tert-butyl, “iBu” refers to isobutyl, “Pn”refers to and “NPn” refers to neopentyl. In some embodiments, alkylgroups are C₁-C₅- or C₁-C₄-alkyl groups.

The term “allyl” refers to an allyl (C₃H₅) ligand which is bound to ametal center. As used herein, the allyl ligand has a resonating doublebond and all three carbon atoms of the allyl ligand are bound to themetal center in η³-coordination by π bonding. Therefore, the complexesof the invention are π complexes. Both of these features are representedby the dashed bonds. When the allyl portion is substituted by one Xgroup, the X¹ group replaces an allylic hydrogen to become [X¹C₃H₄];when substituted with two X groups X¹ and X², it becomes [X¹X²C₃H₃]where X¹ and X² are the same or different, and so forth.

The term “silyl” refers to a —SiZ¹Z²Z³ radical, where each of Z¹, Z²,and Z³ is independently selected from the group consisting of hydrogenand optionally substituted alkyl, alkenyl, alkynyl, aryl, alkoxy,aryloxy, amino, and combinations thereof.

The term “trialkylsilyl” refers to a —SiZ⁴Z⁵Z⁶ radical, wherein Z⁵, Z⁶,and Z⁷ are alkyl, and wherein Z⁵, Z⁶, and Z⁷ can be the same ordifferent alkyls. Non-limiting examples of a trialkylsilyl includetrimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS) andtert-butyldimethylsilyl (TBDMS).

Deposition of some metals, including scandium and yttrium, can bedifficult to achieve due to thermal stability issues, being eitherunstable or too stable for deposition. The organometallic complexesdisclosed in the embodiments of the invention allow for control ofphysical properties as well as provide for increased stability andsimple high yield synthesis. In this regard, the metal complexesprovided herein are excellent candidates for preparation of thinmetal-containing films in various vapor deposition processes.

Therefore, according to one aspect, a metal complex of Formula I isprovided: [(R¹)_(n)Cp]₂M¹L¹ (I), wherein M¹ is a Group 3 metal or alanthanide; each R¹ is independently hydrogen, C₁-C₅-alkyl or silyl; nis 1, 2, 3, 4, or 5; Cp is cyclopentadienyl ring; and L¹ is selectedfrom the group consisting of: NR²R³; N(SiR⁴R⁵R⁶)₂; 3,5-R⁷R⁸—C₃HN₂;1-(R³²)C₃H₄; 1-R³³-3-R³⁴—C₃H₃; R³⁵, R³⁶—C₃HO₂; R¹²N═C—C—NR¹³;R¹⁴R¹⁵N—CH₂—CH₂—NR¹⁶—CH₂—CH₂—NR¹⁷R¹⁸; andR¹⁹O—CH₂—CH₂—NR²⁰—CH₂—CH₂—OR²¹; wherein R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹²,R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ are each independentlyhydrogen or C₁-C₅-alkyl and R³², R³³, R³⁴, R³⁵, and R³⁶ are eachindependently alkyl or silyl.

In some embodiments, M¹ may be selected from the group consisting ofscandium, yttrium and lanthanum. In other embodiments, M¹ may beselected from the group consisting of scandium and yttrium. Inparticular, M¹ may be scandium.

In other embodiments, when M¹ is yttrium and L¹ is 3,5-R⁷R⁸—C₃HN₂, R¹ isC₁-C₅-alkyl or silyl and/or wherein when M¹ is yttrium and L¹ isN(SiR⁴R⁵R⁶)₂, n is 1, 2, 3, or 4.

In some embodiments, L¹ is selected from the group consisting of: NR²R³;N(SiR⁴R⁵R⁶)₂; 3,5-R⁷R⁸—C₃HN₂; 1-(R³²)C₃H₄; 1-R³³-3-R³⁴—C₃H₃, and R³⁵,R³⁶—C₃HO₂.

In some embodiments, L¹ is selected from the group consisting of: NR²R³;N(SiR⁴R⁵R⁶)₂; 3,5-R⁷R⁸—C₃HN₂; 1-(SiMe₃)C₃H₄(trimethyl silylallyl);1,3-bis-(SiMe₃)₂C₃H₃(bis-trimethyl silylallyl),6-methyl-2,4-heptanedionate.

R¹, at each occurrence, can be the same or different. For example, if nis 2, 3, 4, or 5, each R¹ may all be hydrogen or all be an alkyl (e.g.,C₁-C₅-alkyl) or all be silyl. Alternatively, if n is 2, 3, 4, or 5, eachR¹ may be different. For example if n is 2, a first R¹ may be hydrogenand a second R¹ may be an alkyl (e.g., C₁-C₅-alkyl) or silyl.

R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰,and R²¹ at each occurrence, can be the same or different. For example,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰,and R²¹ may all be hydrogen or all be an alkyl (e.g., C₁-C₅-alkyl).

In one embodiment, up to and including sixteen of R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ may each behydrogen. For example, at least one of, at least two of, at least threeof, at least four of or at least five of, at least six of, at leastseven of, at least eight of, at least nine of, at least ten of, at leasteleven of, at least twelve of, at least thirteen of, at least fourteenof, at least fifteen of, or at least sixteen of R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹, R¹⁸, R¹⁹, R²⁰, and R²¹ may be hydrogen.

In another embodiment, up to and including sixteen of R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ eachindependently may be an alkyl. For example, at least one of, at leasttwo of, at least three of, at least four of or at least five of, atleast six of, at least seven of, at least eight of, at least nine of, atleast ten of, at least eleven of, at least twelve of, at least thirteenof, at least fourteen of, at least fifteen of, or at least sixteen ofR², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰,and R²¹ may be an alkyl.

R³², R³³, and R³⁴ at each occurrence, can be the same or different. Forexample, R³², R³³, and R³⁴ may all be an alkyl (e.g., C₁-C₅-alkyl) ormay all be silyl (e.g., SiMe₃).

R³⁵ and R³⁶ at each occurrence, can be the same or different. Forexample, R³⁵ and R³⁶ may all be the same or different alkyl (e.g.,C₁-C₅-alkyl), R³⁵ and R³⁶ may all be the same or different silyl (e.g.,SiMe₃) or R³⁵ and R³⁶ may be an alkyl (e.g., C₁-C₅-alkyl) and a silyl(e.g., SiMe₃).

In one embodiment, up to and including two of R³², R³³, R³⁴, R³⁵, andR³⁶ each independently may be alkyl. For example, at least one of or atleast two of R³², R³³, R³⁴, R³⁵, and R³⁶ may be an alkyl.

In another embodiment, up to and including two of R³², R³³, R³⁴, R³⁵,and R³⁶ each independently may be silyl. For example, at least one of orat least two of R³², R³³, R³⁴, R³⁵, and R³⁶ may be an silyl.

The alkyl groups discussed herein can be C₁-C₅-alkyl, C₁-C₇-alkyl,C₁-C₆-alkyl, C₁-C₅-alkyl, C₁-C₄-alkyl, C₁-C₃-alkyl, C₁-C₂-alkyl orC₁-alkyl. In a further embodiment, the alkyl is C₁-C₅-alkyl,C₁-C₄-alkyl, C₁-C₃-alkyl, C₁-C₂-alkyl or C₁-alkyl. The alkyl group maybe straight-chained or branch. In particular, the alkyl isstraight-chained. In a further embodiment the alkyl is selected from thegroup consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, and neopentyl.

The silyl group discussed herein can be, but is not limited toSi(alkyl)₃, Si(alkyl)₂H, and Si(alkyl)H₂, wherein the alkyl is asdescribed above. Examples of the silyl include, but are not limited toSiH₃, SiMeH₂, SiMe₂H, SiMe₃, SiEtH₂, SiEt₂H, SiEt₃, SiPrH₂, SiPr₂H,SiPr₃, SiBuH₂, SiBu₂H, SiBu₃, where “Pr” includes i-Pr and “Bu” includest-Bu.

In some embodiments, each R¹ independently may be hydrogen, C₁-C₄-alkylor silyl. In another embodiment, each R¹ independently may be hydrogen,methyl, ethyl, propyl or silyl. In another embodiment, each R¹independently may be hydrogen, methyl, or ethyl. In particular, each R¹may be methyl.

In some embodiments, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ each independently may be hydrogen orC₁-C₄-alkyl. In other embodiments, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ each independently may behydrogen, methyl, ethyl or propyl. In other embodiments, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ eachindependently may hydrogen, methyl, or ethyl. In particular, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹each independently may be hydrogen or methyl.

In some embodiments, each R¹ independently may be hydrogen, C₁-C₄-alkylor silyl; and R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, and R¹⁸ each independently may be hydrogen orC₁-C₄-alkyl.

In other embodiments, each R¹ independently may be hydrogen, methyl,ethyl, propyl or silyl; and R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ each independently may behydrogen, methyl, ethyl or propyl.

In some embodiments, each R¹ independently may be hydrogen, methyl, orethyl; and R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, and R²¹ each independently may be hydrogen, methyl, orethyl. In another embodiment, each R¹ may be methyl and R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ eachindependently may be hydrogen or methyl.

In some embodiments, R³², R³³, R³⁴, R³⁵, and R³⁶ each independently maybe C₁-C₅-alkyl or silyl. In other embodiments, R³², R³³, R³⁴, R³⁵, andR³⁶ each independently may be C₁-C₄-alkyl or silyl. In otherembodiments, R³², R³³, R³⁴, R³⁵, and R³⁶ each independently may bemethyl, ethyl, propyl or silyl. In other embodiments, R³², R³³, R³⁴,R³⁵, and R³⁶ each independently may be methyl, ethyl or silyl. In otherembodiments, R³², R³³, R³⁴, R³⁵, and R³⁶ each independently may silyl,such as but not limited to, SiH₃, SiMeH₂, SiMe₂H, SiMe₃, SiEtH₂, SiEt₂H,SiEt₃, SiPrH₂, SiPr₂H, SiPr₃, SiBuH₂, SiBu₂H, SiBu₃. In particular, R³²,R³³, R³⁴, R³⁵, and R³⁶ each independently may be SiMe₃. In particular,R³², R³³, and R³⁴, each independently may be SiMe₃. In otherembodiments, R³⁵ and R³⁶ may each independently be C₁-C₄-alkyl,particularly methyl and/or butyl.

In some embodiments, L¹ is selected from the group consisting of: NR²R³;N(SiR⁴R⁵R⁶)₂; 1-(R³²)C₃H₄; and 1-R³³-3-R³⁴—C₃H₃.

In another embodiment, L¹ may be selected from the group consisting of:NR²R³; N(SiR⁴R⁵R⁶)₂; 1-(SiMe₃)C₃H₄; 1,3-bis-(SiMe₃)₂C₃H₃; and R³⁵,R³⁶—C₃HO₂.

In another embodiment, each R¹ independently may be hydrogen,C₁-C₄-alkyl or silyl; and L¹ is NR²R³, wherein R² and R³ eachindependently may be hydrogen or C₁-C₄-alkyl. In another embodiment,each R¹ independently may be hydrogen, methyl, ethyl, propyl or silyl;and R² and R³ each independently may be hydrogen, methyl, ethyl orpropyl. In another embodiment, each R¹ independently may be hydrogen,methyl, or ethyl; and R² and R³ each independently may be hydrogen,methyl, or ethyl. In particular, each R¹ may be methyl; and R² and R³each independently may be hydrogen, methyl, or ethyl.

In another embodiment, each R¹ independently may be hydrogen,C₁-C₄-alkyl or silyl; and L¹ is N(SiR⁴R⁵R⁶)₂, wherein R⁴, R⁵, and R⁶each independently may be hydrogen or C₁-C₄-alkyl. In anotherembodiment, each R¹ independently may be hydrogen, methyl, ethyl, propylor silyl; and R⁴, R⁵, and R⁶ each independently may be hydrogen, methyl,ethyl or propyl. In another embodiment, each R¹ independently may behydrogen, methyl, or ethyl; and R⁴, R⁵, and R⁶ each independently may behydrogen, methyl, or ethyl. In particular, each R¹ may be methyl; andR⁴, R⁵, and R⁶ each independently may be hydrogen, methyl, or ethyl.

In some embodiments, each R¹ independently may be hydrogen, C₁-C₄-alkylor silyl; and L¹ may be 3,5-R⁷R⁸—C₃HN₂, wherein R⁷ and R⁸ eachindependently may be hydrogen or C₁-C₅-alkyl. In other embodiments, eachR¹ independently may be hydrogen, methyl, ethyl, propyl or silyl. Inother embodiments, each R¹ independently may be hydrogen, methyl, orethyl. In particular, each R¹ may be methyl. In other embodiments, R⁷and R⁸ each independently may be hydrogen or C₁-C₄-alkyl or hydrogen. Inother embodiments, R⁷ and R⁸ each independently may be methyl, ethyl,propyl or hydrogen. In particular, R⁷ and R⁸ each independently may bemethyl or ethyl.

In some embodiments, each R¹ independently may be hydrogen, C₁-C₄-alkylor silyl; and L¹ may be 1-(R³²)C₃H₄, wherein R³² may be C₁-C₅-alkyl orsilyl. In another embodiment, R³² may be C₁-C₄-alkyl or silyl. In otherembodiments, each R¹ independently may be hydrogen, methyl, ethyl orsilyl and R³² may be silyl. In another embodiment, each R¹ independentlymay be hydrogen, methyl or ethyl and R³² may be a silyl, such as but notlimited to, SiH₃, SiMeH₂, SiMe₂H, SiMe₃, SiEtH₂, SiEt₂H, SiEt₃, SiPrH₂,SiPr₂H, SiPr₃, SiBuH₂, SiBu₂H, SiBu₃. In particular, each R¹independently may be methyl or ethyl and R³² may be SiMe₃.

In other embodiments, each R¹ independently may be hydrogen, C₁-C₄-alkylor silyl; and L¹ may be 1-R³³-3-R³⁴—C₃H₃, wherein R³³ and R³⁴ may beC₁-C₅-alkyl or silyl. In another embodiment, each R¹ independently maybe hydrogen, methyl, ethyl or silyl and R³³ and R³⁴ may eachindependently be C₁-C₄-alkyl or silyl and R³² may be silyl. In anotherembodiment, each R¹ independently may be hydrogen, methyl or ethyl andR³³ and R³⁴ may each independently be a silyl, such as but not limitedto, SiH₃, SiMeH₂, SiMe₂H, SiMe₃, SiEtH₂, SiEt₂H, SiEt₃, SiPrH₂, SiPr₂H,SiPr₃, SiBuH₂, SiBu₂H, SiBu₃. In particular, each R¹ independently maybe methyl or ethyl and R³³ and R³⁴ may be SiMe₃.

In other embodiments, each R¹ independently may be hydrogen, C₁-C₄-alkylor silyl; and L¹ may be R³⁵, R³⁶—C₃HO₂, wherein R³⁵ and R³⁶ may beC₁-C₅-alkyl or silyl. In another embodiment, each R¹ independently maybe hydrogen, methyl, ethyl or silyl and R³⁵ and R³⁶ may eachindependently be C₁-C₄-alkyl or silyl. In another embodiment, each R¹independently may be hydrogen, methyl or ethyl and R³⁵ and R³⁶ may eachindependently be a silyl, such as but not limited to, SiH₃, SiMeH₂,SiMe₂H, SiMe₃, SiEtH₂, SiEt₂H, SiEt₃, SiPrH₂, SiPr₂H, SiPr₃, SiBuH₂,SiBu₂H, SiBu₃. In another embodiment, each R¹ independently may behydrogen, methyl or ethyl and R³⁵ and R³⁶ may each independently beC₁-C₄-alkyl, particularly methyl and/or butyl. In particular, each R¹independently may be methyl or ethyl and R³⁵ and R³⁶ may independentlyeach be methyl or butyl. In particular, each R¹ independently may bemethyl or ethyl and R³⁵ and R³⁶ may be SiMe₃.

Examples of metal complexes corresponding in structure to Formula I areprovided in Table 1.

TABLE 1 Complexes of Formula I Sc(MeCp)₂[1-(SiMe₃)C₃H₄] (1)Sc(MeCp)₂[1,3-bis-(SiMe₃)₂C₃H₃] (2) Sc(MeCp)₂[N(SiMe₃)₂] (3)Sc(MeCp)₂(3,5-Me₂-C₃HN₂) (4)

(5)

(6)

(7) Y(MeCp)₂(3,5-MePn-C₃HN₂) (8)

(9)

(10)

In one embodiment, a mixture of two or more organometallic complexes ofFormula I is provided.

In another embodiment, a metal complex of Formula II is provided:[((R⁹)_(n)Cp)₂M²L²]₂ (II), wherein M² is a Group 3 metal or alanthanide; each R⁹ is independently hydrogen or C₁-C₅-alkyl; n is 1, 2,3, 4 or 5; Cp is cyclopentadienyl ring; and L² is selected from thegroup consisting of: Cl; F; Br; I; 3,5-R¹⁰R¹¹—C₃HN₂; R²²N═C—C—NR²³;R²⁴R²⁵N—CH₂—NR²⁶—CH₂—NR²⁷R²⁸, and R²⁹O—CH₂—NR³⁰—CH₂—OR³¹; wherein R¹,R¹¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, and R³¹ are eachindependently hydrogen or C₁-C₅-alkyl.

In some embodiments, M² may be selected from the group consisting ofscandium, yttrium and lanthanum. In other embodiments, M² may beselected from the group consisting of scandium and yttrium. Inparticular, M² may be scandium.

In other embodiments, wherein when M² is scandium and L² is Cl, R⁹ isC₁-C₅-alkyl.

In some embodiments, L² is selected from the group consisting of: Cl; F;Br; I; and 3,5-R¹⁰R¹¹—C₃HN₂

R⁹, at each occurrence, can be the same or different. For example, if nis 2, 3, 4, or 5, each R⁹ may all be hydrogen or all be an alkyl (e.g.,C₁-C₅-alkyl). Alternatively, if n is 2, 3, 4, or 5, each R¹ may bedifferent. For example if n is 2, a first R⁹ may be hydrogen and asecond R⁹ may be an alkyl (e.g., C₁-C₅-alkyl).

R¹⁰, R¹¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, and R³¹, at eachoccurrence, can be the same or different. For example, R¹⁰, R¹¹, R²²,R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, and R³¹ may all be hydrogen orall be an alkyl (e.g., C₁-C₅-alkyl).

In one embodiment, up to and including eleven of R¹⁰, R¹¹, R²², R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, and R³¹ may each be hydrogen. Forexample, at least one of, at least two of, at least three of, at leastfour of or at least five of, at least six of, at least seven of, atleast eight of, at least nine of, at least ten of, at least eleven ofR¹⁰, R¹¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, and R³¹ may behydrogen.

In another embodiment, up to and including eleven of R¹⁰, R¹¹, R²², R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, and R³¹ each independently may be analkyl. For example, at least one of, at least two of, at least three of,at least four of or at least five of, at least six of, at least sevenof, at least eight of, at least nine of, at least ten of, at leasteleven of R¹⁰, R¹¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, and R³¹may be an alkyl.

The alkyl groups discussed herein can be C₁-C₅-alkyl, C₁-C₇-alkyl,C₁-C₆-alkyl, C₁-C₅-alkyl, C₁-C₄-alkyl, C₁-C₃-alkyl, C₁-C₂-alkyl orC₁-alkyl. In a further embodiment, the alkyl is C₁-C₅-alkyl,C₁-C₄-alkyl, C₁-C₃-alkyl, C₁-C₂-alkyl or C₁-alkyl. The alkyl group maybe straight-chained or branch. In particular, the alkyl isstraight-chained. In a further embodiment the alkyl is selected from thegroup consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, and neopentyl.

In some embodiments, each R⁹ independently may be C₁-C₅-alkyl. In otherembodiments, each R⁹ independently may be hydrogen or C₁-C₄-alkyl. Inanother embodiment, each R⁹ independently may be hydrogen, methyl,ethyl, or propyl. In another embodiment, each R⁹ independently may behydrogen, methyl, or ethyl. In particular, each R⁹ may be methyl.

In a particular embodiment, M² may be scandium and each R⁹ independentlymay be a C₁-C₄-alkyl. In another embodiment, M² may be scandium, L² maybe Cl and each R⁹ independently may be methyl, ethyl or propyl. Inparticular, each R⁹ may independently be methyl or ethyl.

In another particular embodiment, M² may be yttrium and each R⁹independently may be a C₁-C₄-alkyl. In another embodiment, M² may beyttrium, L² may be 3,5-R¹⁰R¹¹—C₃HN₂, each R⁹ independently may bemethyl, ethyl or propyl and R¹⁰ and R⁹ each independently may be aC₁-C₅-alkyl. In particular, each R⁹ independently may be methyl orethyl.

Examples of metal complexes corresponding in structure to Formula II areprovided in Table 2.

TABLE 2 Complexes of Formula II [Sc(MeCp)₂]Cl]₂[Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂ (11) (12)

Additional other metal complexes provided herein includeY(MeCp)₂(3,5-tBu₂-C₃HN₂)(THF), Y(MeCp)₂(3,5-MePn-C₃HN₂)(THF), andY(MeCp)₂(3,5-tBu, iBu-C₃HN₂)(THF). As used herein, “THF” refers totetrahydrofuran

The metal complexes provided herein may be prepared, for example, asshown below in Scheme A.

The metal complexes provided herein may be used to preparemetal-containing films such as, for example, elemental scandium,elemental yttrium, scandium oxide, yttrium oxide, scandium nitride,yttrium nitride and scandium silicide and yttrium silicide films. Thus,according to another aspect, a method of forming a metal-containing filmby a vapor deposition process is provided. The method comprisesvaporizing at least one organometallic complex corresponding instructure to Formula I, Formula II, or a combination thereof, asdisclosed herein. For example, this may include (1) vaporizing the atleast one complex and (2) delivering the at least one complex to asubstrate surface or passing the at least one complex over a substrate(and/or decomposing the at least one complex on the substrate surface).

A variety of substrates can be used in the deposition methods disclosedherein. For example, metal complexes as disclosed herein may bedelivered to, passed over, or deposited on a variety of substrates orsurfaces thereof such as, but not limited to, silicon, crystallinesilicon, Si(100), Si(111), silicon oxide, glass, strained silicon,silicon on insulator (SOI), doped silicon or silicon oxide(s) (e.g.,carbon doped silicon oxides), silicon nitride, germanium, galliumarsenide, tantalum, tantalum nitride, aluminum, copper, ruthenium,titanium, titanium nitride, tungsten, tungsten nitride, and any numberof other substrates commonly encountered in nanoscale device fabricationprocesses (e.g., semiconductor fabrication processes). As will beappreciated by those of skill in the art, substrates may be exposed to apretreatment process to polish, etch, reduce, oxidize, hydroxylate,anneal and/or bake the substrate surface. In one or more embodiments,the substrate surface contains a hydrogen-terminated surface.

In certain embodiments, the metal complex may be dissolved in a suitablesolvent such as a hydrocarbon or an amine solvent to facilitate thevapor deposition process. Appropriate hydrocarbon solvents include, butare not limited to, aliphatic hydrocarbons, such as hexane, heptane andnonane; aromatic hydrocarbons, such as toluene and xylene; and aliphaticand cyclic ethers, such as diglyme, triglyme, and tetraglyme. Examplesof appropriate amine solvents include, without limitation, octylamineand N,N-dimethyldodecylamine. For example, the metal complex may bedissolved in toluene to yield a solution with a concentration from about0.05 M to about 1 M.

In another embodiment, the at least one metal complex may be delivered“neat” (undiluted by a carrier gas) to a substrate surface.

In one embodiment, the vapor deposition process is chemical vapordeposition.

In another embodiment, the vapor deposition process is atomic layerdeposition.

The ALD and CVD methods encompass various types of ALD and CVD processessuch as, but not limited to, continuous or pulsed injection processes,liquid injection processes, photo-assisted processes, plasma-assisted,and plasma-enhanced processes. For purposes of clarity, the methods ofthe present technology specifically include direct liquid injectionprocesses. For example, in direct liquid injection CVD (“DLI-CVD”), asolid or liquid metal complex may be dissolved in a suitable solvent andthe solution formed therefrom injected into a vaporization chamber as ameans to vaporize the metal complex. The vaporized metal complex is thentransported/delivered to the substrate surface. In general, DLI-CVD maybe particularly useful in those instances where a metal complex displaysrelatively low volatility or is otherwise difficult to vaporize.

In one embodiment, conventional or pulsed CVD is used to form ametal-containing film vaporizing and/or passing the at least one metalcomplex over a substrate surface. For conventional CVD processes see,for example Smith, Donald (1995). Thin-Film Deposition: Principles andPractice. McGraw-Hill.

In one embodiment, CVD growth conditions for the metal complexesdisclosed herein include, but are not limited to:

-   -   a. Substrate temperature: 50-600° C.    -   b. Evaporator temperature (metal precursor temperature): 0-200°        C.    -   c. Reactor pressure: 0-100 Torr    -   d. Argon or nitrogen carrier gas flow rate: 0-500 sccm    -   e. Oxygen flow rate: 0-500 sccm    -   f. Hydrogen flow rate: 0-500 sccm    -   g. Run time: will vary according to desired film thickness

In another embodiment, photo-assisted CVD is used to form ametal-containing film by vaporizing and/or passing at least one metalcomplex disclosed herein over a substrate surface.

In a further embodiment, conventional (i.e., pulsed injection) ALD isused to form a metal-containing film by vaporizing and/or passing atleast one metal complex disclosed herein over a substrate surface. Forconventional ALD processes see, for example, George S. M., et al. J.Phys. Chem., 1996, 100, 13121-13131.

In another embodiment, liquid injection ALD is used to form ametal-containing film by vaporizing and/or passing at least one metalcomplex disclosed herein over a substrate surface, wherein at least onemetal complex is delivered to the reaction chamber by direct liquidinjection as opposed to vapor draw by a bubbler. For liquid injectionALD processes see, for example, Potter R. J., et al., Chem. Vap.Deposition, 2005, 11(3), 159-169.

Examples of ALD growth conditions for metal complexes disclosed hereininclude, but are not limited to:

-   -   a. Substrate temperature: 0-400° C.    -   b. Evaporator temperature (metal precursor temperature): 0-200°        C.    -   c. Reactor pressure: 0-100 Torr    -   d. Argon or nitrogen carrier gas flow rate: 0-500 sccm    -   e. Reactive gas flow rate: 0-500 sccm    -   f. Pulse sequence (metal complex/purge/reactive gas/purge): will        vary according to chamber size    -   g. Number of cycles: will vary according to desired film        thickness

In another embodiment, photo-assisted ALD is used to form ametal-containing film by vaporizing and/or passing at least one metalcomplex disclosed herein over a substrate surface. For photo-assistedALD processes see, for example, U.S. Pat. No. 4,581,249.

In another embodiment, plasma-assisted or plasma-enhanced ALD is used toform a metal-containing film by vaporizing and/or passing at least onemetal complex disclosed herein over a substrate surface.

In another embodiment, a method of forming a metal-containing film on asubstrate surface comprises: during an ALD process, exposing a substrateto a vapor phase metal complex according to one or more of theembodiments described herein, such that a layer is formed on the surfacecomprising the metal complex bound to the surface by the metal center(e.g., nickel); during an ALD process, exposing the substrate havingbound metal complex with a co-reactant such that an exchange reactionoccurs between the bound metal complex and co-reactant, therebydissociating the bound metal complex and producing a first layer ofelemental metal on the surface of the substrate; and sequentiallyrepeating the ALD process and the treatment.

The reaction time, temperature and pressure are selected to create ametal-surface interaction and achieve a layer on the surface of thesubstrate. The reaction conditions for the ALD reaction will be selectedbased on the properties of the metal complex. The deposition can becarried out at atmospheric pressure but is more commonly carried out ata reduced pressure. The vapor pressure of the metal complex should below enough to be practical in such applications. The substratetemperature should be high enough to keep the bonds between the metalatoms at the surface intact and to prevent thermal decomposition ofgaseous reactants. However, the substrate temperature should also behigh enough to keep the source materials (i.e., the reactants) in thegaseous phase and to provide sufficient activation energy for thesurface reaction. The appropriate temperature depends on variousparameters, including the particular metal complex used and thepressure. The properties of a specific metal complex for use in the ALDdeposition methods disclosed herein can be evaluated using methods knownin the art, allowing selection of appropriate temperature and pressurefor the reaction. In general, lower molecular weight and the presence offunctional groups that increase the rotational entropy of the ligandsphere result in a melting point that yields liquids at typical deliverytemperatures and increased vapor pressure.

A metal complex for use in the deposition methods will have all of therequirements for sufficient vapor pressure, sufficient thermal stabilityat the selected substrate temperature and sufficient reactivity toproduce a reaction on the surface of the substrate without unwantedimpurities in the thin film. Sufficient vapor pressure ensures thatmolecules of the source compound are present at the substrate surface insufficient concentration to enable a complete self-saturating reaction.Sufficient thermal stability ensures that the source compound will notbe subject to the thermal decomposition which produces impurities in thethin film.

Thus, the metal complexes disclosed herein utilized in these methods maybe liquid, solid, or gaseous. Typically, the metal complexes are liquidsor solids at ambient temperatures with a vapor pressure sufficient toallow for consistent transport of the vapor to the process chamber.

In one embodiment, an elemental metal, a metal nitride, a metal oxide,or a metal silicide film can be formed by delivering for deposition atleast one metal complex as disclosed herein, independently or incombination with a co-reactant. In this regard, the co-reactant may bedeposited or delivered to or passed over a substrate surface,independently or in combination with the at least one metal complex. Aswill be readily appreciated, the particular co-reactant used willdetermine the type of metal-containing film is obtained. Examples ofsuch co-reactants include, but are not limited to hydrogen, hydrogenplasma, oxygen, air, water, an alcohol, H₂O₂, N₂O, ammonia, a hydrazine,a borane, a silane, ozone, or a combination of any two or more thereof.Examples of suitable alcohols include, without limitation, methanol,ethanol, propanol, isopropanol, tert-butanol, and the like. Examples ofsuitable boranes include, without limitation, hydridic (i.e., reducing)boranes such as borane, diborane, triborane and the like. Examples ofsuitable silanes include, without limitation, hydridic silanes such assilane, disilane, trisilane, and the like. Examples of suitablehydrazines include, without limitation, hydrazine (N₂H₄), a hydrazineoptionally substituted with one or more alkyl groups (i.e., analkyl-substituted hydrazine) such as methylhydrazine,tert-butylhydrazine, N,N- or N,N′-dimethylhydrazine, a hydrazineoptionally substituted with one or more aryl groups (i.e., anaryl-substituted hydrazine) such as phenylhydrazine, and the like.

In one embodiment, the metal complexes disclosed herein are delivered tothe substrate surface in pulses alternating with pulses of anoxygen-containing co-reactant as to provide metal oxide films. Examplesof such oxygen-containing co-reactants include, without limitation, H₂O,H₂O₂, O₂, ozone, air, i-PrOH, t-BuOH, or N₂O.

In other embodiments, a co-reactant comprises a reducing reagent such ashydrogen. In such embodiments, an elemental metal film is obtained. Inparticular embodiments, the elemental metal film consists of, orconsists essentially of, pure metal. Such a pure metal film may containmore than about 80, 85, 90, 95, or 98% metal. In even more particularembodiments, the elemental metal film is a scandium film or a yttriumfilm.

In other embodiments, a co-reactant is used to form a metal nitride filmby delivering for deposition at least one metal complex as disclosedherein, independently or in combination, with a co-reactant such as, butnot limited to, ammonia, a hydrazine, and/or other nitrogen-containingcompounds (e.g., an amine) to a reaction chamber. A plurality of suchco-reactants may be used. In further embodiments, the metal nitride filmis a nickel nitride film.

In another embodiment, a mixed-metal film can be formed by a vapordeposition process which vaporizes at least one metal complex asdisclosed herein in combination, but not necessarily at the same time,with a second metal complex comprising a metal other than that of the atleast one metal complex disclosed herein.

In a particular embodiment, the methods of the present technology areutilized for applications such as dynamic random access memory (DRAM)and complementary metal oxide semi-conductor (CMOS) for memory and logicapplications, on substrates such as silicon chips.

Any of the metal complexes disclosed herein may be used to prepare thinfilms of the elemental metal, metal oxide, metal nitride, and/or metalsilicide. Such films may find application as oxidation catalysts, anodematerials (e.g., SOFC or LIB anodes), conducting layers, sensors,diffusion barriers/coatings, super- and non-superconductingmaterials/coatings, tribological coatings, and/or, protective coatings.It is understood by one of ordinary skill in the art that the filmproperties (e.g., conductivity) will depend on a number of factors, suchas the metal(s) used for deposition, the presence or absence ofco-reactants and/or co-complexes, the thickness of the film created, theparameters and substrate employed during growth and subsequentprocessing.

Fundamental differences exist between the thermally-driven CVD processand the reactivity-driven ALD process. The requirements for precursorproperties to achieve optimum performance vary greatly. In CVD a cleanthermal decomposition of the complex to deposit the required speciesonto the substrate is critical. However, in ALD such a thermaldecomposition is to be avoided at all costs. In ALD, the reactionbetween the input reagents must be rapid at the surface resulting information of the target material on the substrate. However, in CVD, anysuch reaction between species is detrimental due to their gas phasemixing before reaching the substrate, which could lead to particleformation. In general it is accepted that good CVD precursors do notnecessarily make good ALD precursors due to the relaxed thermalstability requirement for CVD precursors. In this invention, Formula Imetal complexes possess enough thermal stability and reactivity towardselect co-reactants to function as ALD precursors, and they possessclean decomposition pathways at higher temperatures to form desiredmaterials through CVD processes as well. Therefore, the metal complexesdescribed by Formula I are advantageously useful as viable ALD and CVDprecursors.

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment ofthe present technology. Thus, the appearances of the phrases such as “inone or more embodiments,” “in certain embodiments,” “in one embodiment”or “in an embodiment” in various places throughout this specificationare not necessarily referring to the same embodiment of the presenttechnology. Furthermore, the particular features, structures, materials,or characteristics may be combined in any suitable manner in one or moreembodiments.

Although the present technology herein has been described with referenceto particular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent technology. It will be apparent to those skilled in the art thatvarious modifications and variations can be made to the method andapparatus of the present technology without departing from the spiritand scope of the present technology. Thus, it is intended that thepresent technology include modifications and variations that are withinthe scope of the appended claims and their equivalents. The presenttechnology, thus generally described, will be understood more readily byreference to the following examples, which is provided by way ofillustration and is not intended to be limiting.

The invention can additionally or alternatively include one or more ofthe following embodiments.

Embodiment 1

A metal complex corresponding in structure to Formula I:[(R¹)_(n)Cp]₂M¹L¹ (I), wherein M¹ is a Group 3 metal or a lanthanide(e.g., scandium, yttrium and lanthanum); each R¹ is independentlyhydrogen, C₁-C₅-alkyl or silyl; n is 1, 2, 3, 4, or 5; Cp iscyclopentadienyl ring; and L¹ is selected from the group consisting of:NR²R³; N(SiR⁴R⁵R⁶)₂; 3,5-R⁷R⁸—C₃HN₂; 1-(R³²)C₃H₄; 1-R³³-3-R³⁴—C₃H₃; andR³⁵, R³⁶—C₃HO₂; R¹²N═C—C—NR¹³; R¹⁴R¹⁵N—CH₂—CH₂—NR¹⁶—CH₂—CH₂—NR¹⁷R¹⁸; andR¹⁹O—CH₂—CH₂—NR²⁰—CH₂—CH₂—OR²¹; wherein R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹²,R¹³, R⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ are each independentlyhydrogen or C₁-C₅-alkyl; and R³², R³³, R³⁴, R³⁵, and R³⁶ are eachindependently alkyl or silyl; optionally, wherein when M¹ is yttrium andL¹ is 3,5-R⁷R⁸—C₃HN₂, R¹ is C₁-C₅-alkyl or silyl; and optionally,wherein when M¹ is yttrium and L¹ is N(SiR⁴R⁵R⁶)₂, n is 1, 2, 3, or 4.

Embodiment 2

The metal complex of embodiment 1, wherein each R¹ is independentlyhydrogen, C₁-C₄-alkyl or silyl; and R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ areeach independently hydrogen or C₁-C₄-alkyl; and R³², R³³, R³⁴, R³⁵, andR³⁶ are each independently C₁-C₅-alkyl or silyl.

Embodiment 3

The metal complex of embodiment 1 or 2, wherein each R¹ is independentlyhydrogen, methyl, ethyl, propyl or silyl, preferably hydrogen, methyl orethyl, more preferably methyl; and R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ areeach independently hydrogen, methyl, ethyl or propyl, preferablyhydrogen methyl or ethyl, more preferably hydrogen or methyl; and R³²,R³³, R³⁴, R³⁵, and R³⁶ are each independently C₁-C₄-alkyl or silyl,preferably methyl, ethyl, propyl or silyl, more preferably SiMe₃.

Embodiment 4

The metal complex of any one of the previous embodiments, wherein eachR¹ is independently hydrogen, C₁-C₄-alkyl or silyl; and L¹ is NR²R³,wherein R² and R³ are each independently hydrogen or C₁-C₄-alkyl.

Embodiment 5

The metal complex of embodiment 4, wherein each R¹ is independentlyhydrogen, methyl, ethyl, propyl or silyl, preferably hydrogen, methyl,or ethyl, more preferably methyl; and R² and R³ are each independentlyhydrogen, methyl, ethyl or propyl, preferably hydrogen, methyl or ethyl.

Embodiment 6

The metal complex of any one of the previous embodiments, wherein eachR¹ is independently hydrogen, C₁-C₄-alkyl or silyl; and L¹ isN(SiR⁴R⁵R⁶)₂, wherein R⁴, R⁵, and R⁶ are each independently hydrogen orC₁-C₄-alkyl.

Embodiment 7

The metal complex of embodiment 6, wherein each R¹ is independentlyhydrogen, methyl, ethyl, propyl or silyl, preferably hydrogen, methyl,or ethyl, more preferably methyl; and R⁴, R⁵, and R⁶ are eachindependently hydrogen, methyl, ethyl or propyl, preferably hydrogen,methyl or ethyl.

Embodiment 8

The metal complex of any one of the previous embodiments, wherein eachR¹ is independently hydrogen, C₁-C₄-alkyl or silyl; and L¹ is3,5-R⁷R⁸—C₃HN₂, wherein R⁷ and R⁸ are each independently hydrogen orC₁-C₅-alkyl.

Embodiment 9

The metal complex of embodiment 8, wherein each R¹ is independentlyhydrogen, methyl, ethyl, propyl or silyl, preferably hydrogen, methyl,or ethyl, more preferably methyl.

Embodiment 10

The metal complex of any one of the previous embodiments, wherein eachR¹ is independently hydrogen, C₁-C₄-alkyl or silyl, preferably hydrogen,methyl, ethyl or silyl; and L¹ is I—(R³²)C₃H₄, wherein R³² isC₁-C₅-alkyl or silyl, preferably R³² is methyl, ethyl or silyl, morepreferably L¹ is 1-(SiMe₃)C₃H₄.

Embodiment 11

The metal complex of any one of the previous embodiments, wherein eachR¹ is independently hydrogen, C₁-C₄-alkyl or silyl, preferably hydrogen,methyl, ethyl or silyl; and L¹ is 1-R³³-3-R³⁴—C₃H₃, wherein R³³ and R³⁴are each independently C₁-C₅-alkyl or silyl, preferably R³³ and R³⁴ areeach independently methyl, ethyl or silyl, more preferably L¹ is1,3-bis-(SiMe₃)₂C₃H₃.

Embodiment 12

The metal complex of any one of the previous embodiments, wherein eachR¹ is independently hydrogen, C₁-C₄-alkyl or silyl, preferably hydrogen,methyl, ethyl or silyl; and L¹ is R³⁵, R³⁶—C₃HO₂, wherein R³⁵ and R³⁶are each independently C₁-C₅-alkyl or silyl, preferably R³⁵ and R³⁶ areeach independently methyl, ethyl, propyl, butyl, or silyl, morepreferably L¹ is 6-methyl-2,4-heptanedionate, i.e., Me, iBu-C₃HO₂.

Embodiment 13

The metal complex of any one of the previous embodiments, wherein thecomplex is: Sc(MeCp)₂[1-(SiMe₃)C₃H₄]; Sc(MeCp)₂[1,3-bis-(SiMe₃)₂C₃H₃];Sc(MeCp)₂[N(SiMe₃)₂]; Sc(MeCp)₂(3,5-Me₂-C₃HN₂); Sc(MeCp)₂(Me,iBu-C₃HO₂), preferably Sc(MeCp)₂[1-(SiMe₃)C₃H₄];Sc(MeCp)₂[1,3-bis-(SiMe₃)₂C₃H₃]; Sc(MeCp)₂[N(SiMe₃)₂]; andSc(MeCp)₂(3,5-Me₂-C₃HN₂).

Embodiment 14

A metal complex corresponding in structure to Formula II:[((R⁹)_(n)Cp)₂M²L²]₂(II), wherein M² is a Group 3 metal or a lanthanide(e.g., scandium, yttrium and lanthanum); each R⁹ is independentlyhydrogen or C₁-C₅-alkyl; n is 1, 2, 3, 4 or 5; Cp is cyclopentadienylring; and L² is selected from the group consisting of: Cl; F; Br; I;3,5-R¹⁰R¹¹—C₃HN₂; R²²N═C—C—NR²³; R²⁴R²⁵N—CH₂—NR²⁶—CH₂—NR²⁷R²⁸, andR²⁹O—CH₂—NR³⁰—CH₂—OR³¹; wherein R¹⁰, R¹¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷,R²⁸, R²⁹, R³⁰, and R³¹ are each independently hydrogen or C₁-C₅-alkyl,optionally wherein when M² is scandium and L² is Cl, R⁹ is C₁-C₅-alkyl.

Embodiment 15

The metal complex of embodiment 14, wherein each R⁹ is independentlyC₁-C₅-alkyl

Embodiment 16

The metal complex of embodiment 14 or 15, wherein each R⁹ isindependently hydrogen or C₁-C₄-alkyl, preferably hydrogen, methyl,ethyl or propyl, preferably hydrogen, methyl, or ethyl, more preferablymethyl.

Embodiment 17

The metal complex of embodiments 14, 15 or 16, wherein M² is scandium;each R⁹ is independently a C₁-C₄-alkyl, preferably methyl, ethyl orpropyl, more preferably methyl; and preferably L² is Cl.

Embodiment 18

The metal complex of embodiments 14, 15 or 16, wherein M² is yttrium;each R⁹ is independently a C₁-C₅-alkyl, preferably methyl, ethyl orpropyl; more preferably methyl or ethyl; and preferably L² is3,5-R¹⁰R¹¹—C₃HN₂ and each R⁹ is independently.

Embodiment 19

The metal complex of embodiments 14, 15, 16, 17 or 18, wherein thecomplex is [Sc(MeCp)₂]Cl]₂; and [Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂.

Embodiment 20

A method of forming a metal-containing film by a vapor depositionprocess, the method comprising vaporizing at least one metal complexaccording to any one of the previous embodiments.

Embodiment 21

The method of embodiment 20, wherein the vapor deposition process ischemical vapor deposition, preferably pulsed chemical vapor deposition,continuous flow chemical vapor deposition, and/or liquid injectionchemical vapor deposition.

Embodiment 22

The method of embodiment 20, wherein the vapor deposition process isatomic layer deposition, preferably liquid injection atomic layerdeposition or plasma-enhanced atomic layer deposition.

Embodiment 23

The method of any one of embodiments 20, 21 or 22, wherein the metalcomplex is delivered to a substrate in pulses alternating with pulses ofan oxygen source, preferably the oxygen source is selected from thegroup consisting of H₂O, H₂O₂, O₂, ozone, air, i-PrOH, t-BuOH, and N₂O.

Embodiment 24

The method of any one of embodiments 20, 21, 22, or 23 furthercomprising vaporizing at least one co-reactant selected from the groupconsisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, ahydrazine, a borane, a silane, ozone, and a combination of any two ormore thereof, preferably the at least one co-reactant is a hydrazine(e.g., hydrazine (N₂H₄), N,N-dimethylhydrazine).

Embodiment 25

The method of any one of embodiments 20, 21, 22, 23 or 24, wherein themethod is used for a DRAM or CMOS application.

EXAMPLES

Unless otherwise noted, all synthetic manipulations are performed underan inert atmosphere (e.g., purified nitrogen or argon) using techniquesfor handling air-sensitive materials commonly known in the art (e.g.,Schlenk techniques).

Example 1: Preparation of Complex 11 ([Sc(MeCp)₂Cl]₂)

A 500 mL Schlenk flask equipped with a magnetic stirrer was charged withScCl₃ (15.5 g, 0.102 mol) and KMeCp (24.2 g, 0.205 mol) followed byanhydrous diethyl ether (200 mL). The mixture was stirred at roomtemperature (˜18° C. to ˜24° C.) for 12 hours under a nitrogenatmosphere, giving a maroon colored suspension. The solvent was removedunder pressure and the resulting solid was extracted with 5×50 mLtoluene, and filtered through a medium frit. The filtrate was removedfrom the solvent under reduced pressure to afford the final product as ayellow powder (16.4 g, 0.0344 mol, 67% yield). ¹H NMR (C₆D₆) of product:δ 2.02 (12H, MeC₅H₄), 6.09 (8H, MeC₅H₄), 6.24 (8H, MeC₅H₄). ¹³C NMR(C₆D₆) of product: δ 15.4 (MeC₅H₄), 114.4 (MeC₅H₄), 116.0 (MeC₅H₄),124.9 (MeC₅H₄).

Example 2: Preparation of Complex 3 (Sc(MeCp)₂[N(SiMe₃)₂])

A 250 mL Schlenk flask equipped with magnetic stirrer was charged with[Sc(MeCp)₂Cl]₂ (4.6 g, 0.0098 mol) and KN(SiMe₃)₂(3.9 g, 0.020 mol)followed by anhydrous diethyl ether (100 mL). The mixture was stirred atroom temperature (˜18° C. to ˜24° C.) for 12 hours under a nitrogenatmosphere, giving a peach-colored suspension. The solvent was removedunder pressure and the resulting solid was extracted with 3×30 mLhexane, and filtered through a medium frit. The filtrate was removedfrom the solvent under reduced pressure to afford the final product as ayellow powder. (6.7 g, 0.018 mol, 90% yield. ¹H NMR (C₆D₆) of product: δ1.10 (18H, SiMe₃), 2.04 (6H, MeC₅H₄), 5.85 (4H, MeC₅H₄), 6.00 (4H,MeC₅H₄). ¹³C NMR (C₆D₆) of product: δ 4.2 (SiMe₃), 15.7 (MeC₅H₄), 114.3(MeC₅H₄), 115.9 (MeC₅H₄), 125.0 (MeC₅H₄).

Example 3: Synthesis of Complex 2(Sc(MeCp)₂[1,3-bis(trimethylsilyl)allyl])

A 250 mL Schlenk flask equipped with a magnetic stirrer was charged with[Sc(MeCp)₂Cl]₂ (1.0 g, 2.1 mmol) and K(1,3-bis-trimethylsilyl-allyl)(1.05 g, 4.7 mmol) followed by addition of anhydrous diethyl ether (100mL). The mixture was stirred at room temperature (˜18° C. to ˜24° C.)for 12 hours under a nitrogen atmosphere, giving an orange suspension.The solvent was removed under reduced pressure and the resulting solidwas extracted with 3×30 mL hexane, and filtered through a medium frit.The filtrate was removed of solvent under reduced pressure to afford thefinal product as a red liquid. (1.0 g, 2.6 mmol, 62% yield). ¹H NMR(C₆D₆) of product: δ 0.04 (18H, SiMe₃), 1.84 (3H, MeC5H4), 1.94 (3H,MeC₅H₄), 4.90 (2H, allyl CH(TMS)), 5.97 (2H, MeC₅H₄), 6.04 (4H, MeC₅H₄),6.29 (2H, MeC₅H₄), 7.67 (1H, allyl CH).

Example 4: Synthesis of Complex 1 (Sc(MeCp)₂(1-trimethylsilylallyl))

A 250 mL Schlenk flask equipped with a magnetic stirrer was charged with[Sc(MeCp)₂Cl]₂ (5.2 g, 10.9 mmol) and K(trimethylsilyl-allyl) (3.3 g,21.8 mmol) followed by addition of anhydrous diethyl ether (100 mL). Themixture was stirred at room temperature (˜18° C. to ˜24° C.) for 12hours under a nitrogen atmosphere, giving an orange suspension. Thesolvent was removed under reduced pressure and the resulting solid wasextracted with 3×30 mL pentane, and filtered through a medium frit. Thefiltrate was removed of solvent under reduced pressure to afford thefinal product as a red liquid. (3.7 g, 11.7 mmol, 54% yield). ¹H NMR(C₆D₆) of product: δ−0.02 (9H, SiMe₃), 1.82 (6H, MeC₅H₄), 2.29 (1H,allyl CH₂), 4.15 (1H, allyl CH₂), 4.73 (1H, allyl CH(TMS)), 5.94 (8H,MeC₅H₄), 7.47 (1H, allyl CH).

Example 5: Synthesis of Complex 4 (Sc(MeCp)₂(3,5-dimethyl-pyrazolate))

A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with[Sc(MeCp)₂Cl]₂ (12.0 g, 25.1 mmol) and KMe₂Pz (6.75 g, 50.3 mmol)followed by addition of anhydrous THF (150 mL). The mixture was stirredat room temperature (˜18° C. to ˜24° C.) for 12 hours under a nitrogenatmosphere. The solvent was removed under reduced pressure and theresulting yellow sticky solid was extracted with 5×20 mL toluene, andfiltered through a medium frit. The filtrate was removed of solventunder reduced pressure to provide a red oil. Further distillation undervacuum afforded the final product as a light yellow liquid (10.7 g, 35.9mmol, 72% yield). ¹H NMR (C₆D₆) of product: δ 1.85 (6H, MeC₅H₄), 2.28(6H, Me₂Pz), 5.84 (4H, MeC₅H₄), 5.96 (1H, Me₂Pz), 6.20 (4H, MeC₅H₄).

Example 6: Synthesis of Complex 8(Y(MeCp)₂(3-methyl-5-pentyl-pyrazolate))

A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with[Y(MeCp)₂Cl]₂ (9.33 g, 16.5 mmol) and K(Me,Pn)Pz (6.28 g, 33.0 mmol)followed by addition of anhydrous THF (150 mL). The mixture was stirredat room temperature for 12 hours (˜18° C. to ˜24° C.) under a nitrogenatmosphere. The solvent was removed under reduced pressure and theresulting yellow sticky solid was extracted with 5×20 mL toluene, andfiltered through a medium frit. The filtrated was removed of solventunder reduced pressure to provide a red oil. Further distillation undervacuum afforded the final product as a light yellow liquid (7.7 g, 19.3mmol, 58% yield). ¹H NMR (C₆D₆) of product: δ 0.94 (3H, Pentyl), 1.40(4H, Pentyl), 1.75 (2H, Pentyl), 2.16 (6H, MeC₅H₄), 2.17 (3H,^(Me,Pn)Pz), 2.65 (2H, Pentyl), 5.66 (4H, MeC₅H₄), 5.90 (1H,^(Me,Pn)Pz), 5.96 (4H, MeC₅H₄).

Example 7: Synthesis of Complex 9(Sc(MeCp)₂(6-methyl-2,4-heptanedionate))

A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with[Sc(MeCp)₂Cl]₂ (1.0 g, 1.8 mmol) and K(6-Methyl-2,4-heptanedionate)(0.67 g, 3.7 mmol) followed by addition of anhydrous THF (150 mL). Themixture was stirred at room temperature for 12 hours (˜18° C. to ˜24°C.) under a nitrogen atmosphere. The solvent was removed under reducedpressure and the resulting yellow sticky solid was extracted with 3×20mL toluene, and filtered through a medium frit. The filtrated wasremoved of solvent under reduced pressure to provide an orange oil (0.8g, 2.1 mmol, 58% yield). ¹H NMR (C₆D₆) of product: δ 0.89 (6H, ^(i)Bu),1.71 (3H, Me), 1.89 (2H, ^(i)Bu), 2.03 (6H, MeC₅H₄), 2.04 (1H, ^(i)Bu),5.24 (1H, diketonate), 5.85 (4H, MeC₅H₄), 6.05 (2H, MeC₅H₄), 6.14 (2H,MeC₅H₄).

Example 8: Synthesis of Complex 10(Y(MeCp)₂(6-Methyl-2,4-heptanedionate))

A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with[Y(MeCp)₂Cl]₂ (1.5 g, 2.4 mmol) and K(6-Methyl-2,4-heptanedionate) (0.89g, 4.9 mmol) followed by addition of anhydrous THF (150 mL). The mixturewas stirred at room temperature for 12 hours (˜18° C. to ˜24° C.) undera nitrogen atmosphere. The solvent was removed under reduced pressureand the resulting yellow sticky solid was extracted with 3×20 mLtoluene, and filtered through a medium frit. The filtrated was removedof solvent under reduced pressure to provide an orange oil (1.2 g, 2.9mmol, 60% yield). ¹H NMR (C₆D₆) of product: δ 0.89 (6H, ^(i)Bu), 1.72(3H, Me), 1.91 (2H, ^(i)Bu), 2.04 (1H, ^(i)Bu), 2.10 (6H, MeC₅H₄), 5.25(1H, diketonate), 5.95 (4H, MeC₅H₄), 6.10 (2H, MeC₅H₄), 6.15 (2H,MeC₅H₄).

Example 9: ALD of Sc₂O₃ Film Using Complex 4(Sc(MeCp)₂(3,5-dimethyl-pyrazolate)) and Water

Sc(MeCp)₂(3,5-dimethyl-pyrazolate) was heated to 100-115° C. in astainless steel bubbler and delivered into an ALD reactor using about 20sccm of nitrogen as the carrier gas, and pulsed for about 2 secondsfollowed by a ˜28-58 second purge. A pulse of water vapor (I second) wasthen delivered from a room temperature cylinder of water followed by a60-second nitrogen purge. A needle valve was present between thedeposition chamber and the water cylinder, and was adjusted so as tohave an adequate water vapor dose. The scandium oxide was deposited atabout 175-300° C. for up to 300 cycles onto silicon chips having a thinlayer of native oxide, SiO₂. The film was cooled down in the reactor toabout 60° C. under vacuum with nitrogen purge before unloading. Filmthicknesses in the range of 60-260 Å were obtained, and preliminaryresults show a growth rate of ˜1 Angstrom/cycle. XPS (X-rayPhotoelectron Spectroscopy) analysis confirmed the existence of scandiumoxide with N and C contaminants on the top surface, which were removedduring the XPS analysis. The XPS data in FIGS. 1-14 shows the films haveno more than 1% of any element except the desired scandium and oxygenonce the surface contamination has been removed by sputtering. In thebulk, only Sc and O were detected, and the stoichiometry measuredmatched the theoretical composition of Sc₂O₃.

Example 10: ALD of Y₂O₃ Film Using Complex 12([Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂) General Methods

[Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂ was heated to 130-180° C. in a stainlesssteel bubbler, delivered into a cross-flow ALD reactor using nitrogen asa carrier gas and deposited by ALD using water. H₂O was delivered byvapor draw from a stainless steel ampule at room temperature. Siliconchips having a native SiO₂ layer in the range of 14-17 Å thick were usedas substrates. As-deposited films were used for thickness and opticalproperty measurements using an optical ellipsometer. Selected sampleswere analyzed by XPS for film composition and impurity concentrations.

Example 10a

[Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂ was heated to 170° C., delivered into an ALDreactor using 20 sccm of nitrogen as the carrier gas, and pulsed for 7seconds from a bubbler followed by a 20 second of N₂ purge, followed bya 0.015 second pulse of H₂O and 90 second of N₂ purge in each ALD cycle,and deposited at multiple temperatures from 125 to 250° C. for 200 ormore cycles. As-deposited films were cooled down in the reactor to ˜80°C. under nitrogen purge before unloading. Film thickness in the range of150 to 420 Å was deposited. Growth rate per cycle data at a fixedreactor inlet position were plotted in FIG. 15.

The curve in FIG. 15 indicates that the growth rate of Y₂O₃ from anun-optimized H₂O ALD process appeared to be temperature dependent underthe same deposition conditions. The higher the temperature, the higherthe growth rate. Further tests revealed that the growth rate at highertemperatures appeared to be affected by the H₂O purge time, which may bedue to initial formation of Y(OH)₃ and/or strong absorption of H₂O bythe Y₂O₃ film at higher temperatures. For example, no saturation wasreached even after 120 seconds of H₂O purge at 200° C., while itsdependence on the H₂O purge time is much smaller at ˜150° C. or lower asshown in FIG. 16.

Example 10b

[Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂ was heated to 170-176° C., delivered into anALD reactor using 20 sccm of nitrogen as the carrier gas, and pulsedfrom 3 to 13 seconds from a bubbler to generate various precursor doses,followed by a 60 second of N₂ purge, then by a 0.015 second pulse of H₂Oand 30 second of N₂ purge in each ALD cycle, and deposited at 135° C.for 350 cycles. The film thickness was monitored at 3 differentpositions in the cross-flow reactor along the precursor/carrier gas flowdirection, the precursor inlet, the reactor center, and precursoroutlet. Growth rate per cycle data are plotted in FIG. 17.

The saturation of the growth rate per cycle (GPC) at ˜0.79 Å/cycle withthe precursor dose as well as the convergence of the growth rates at thethree different positions suggest that the process at 135° C. is trulyan ALD process with insignificant contribution of any CVD component tothe growth rate. Under optimized saturated growth conditions, anexcellent thickness uniformity of ≤±1.3% over a 6˜7″ diameter area ofthe cross-flow reactor has been achieved.

The full ALD window with deposition temperature has not yet beendetermined. This precursor was thermally stable at higher temperatures≥250° C.

All publications, patent applications, issued patents and otherdocuments referred to in this specification are herein incorporated byreference as if each individual publication, patent application, issuedpatent, or other document was specifically and individually indicated tobe incorporated by reference in its entirety. Definitions that arecontained in text incorporated by reference are excluded to the extentthat they contradict definitions in this disclosure.

The words “comprise”, “comprises”, and “comprising” are to beinterpreted inclusively rather than exclusively.

1. A metal complex corresponding in structure to Formula I:[(R¹)_(n)Cp]₂M¹L¹   (I) wherein M¹ is selected from the group consistingof scandium, yttrium, and lanthanum; each R¹ is independently hydrogen,C₁-C₅-alkyl or silyl; n is 1, 2, 3, 4, or 5; Cp is cyclopentadienylring; and L¹ is selected from the group consisting of: NR²R³;N(SiR⁴R⁵R⁶)₂; 3,5-R⁷R⁸—C₃HN₂; 1-(R³²)C₃H₄; 1-R³³-3-R³⁴—C₃H₃; and R³⁵,R³⁶—C₃HO₂; wherein R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are each independentlyhydrogen or C₁-C₅-alkyl; and R³², R³³, R³⁴, R³⁵, and R³⁶ are eachindependently alkyl or silyl; wherein when M¹ is yttrium and L¹ is3,5-R⁷R⁸—C₃HN₂, R¹ is C₁-C₅-alkyl or silyl; and wherein when M¹ isyttrium and L¹ is N(SiR⁴R⁵R⁶)₂, n is 1, 2, 3, or
 4. 2. (canceled)
 3. Themetal complex of claim 1, wherein each R¹ is independently hydrogen,methyl, ethyl, propyl or silyl; R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are eachindependently hydrogen, methyl, ethyl or propyl; and R³², R³³, R³⁴, R³⁵,and R³⁶ are each independently C₁-C₄-alkyl or silyl.
 4. The metalcomplex of claim 1, wherein each R¹ is independently hydrogen, methyl orethyl; R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are each independently hydrogen,methyl, or ethyl; and R³², R³³, R³⁴, R³⁵, and R³⁶ are each independentlymethyl, ethyl, propyl or silyl.
 5. The metal complex of claim 1, whereineach R¹ is methyl; R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are each independentlyhydrogen or methyl; and R³², R³³, R³⁴, R³⁵, and R³⁶ are each SiMe₃.6-19. (canceled)
 20. The metal complex of claim 1, wherein each R¹ isindependently hydrogen, C₁-C₄-alkyl or silyl; and L¹ is 1-(SiMe₃)C₃H₄ orL¹ is 1,3-bis-(SiMe₃)₂C₃H₃.
 21. (canceled)
 22. (canceled)
 23. (canceled)24. The metal complex of claim 1, wherein the complex is:Sc(MeCp)₂[1-(SiMe₃)C₃H₄]; Sc(MeCp)₂[1,3-bis-(SiMe₃)₂C₃H₃];Sc(MeCp)₂[N(SiMe₃)₂]; and Sc(MeCp)₂(3,5-Me₂-C₃HN₂).
 25. A metal complexcorresponding in structure to Formula II:[((R⁹)_(n)Cp)₂M²L²]₂   (II) wherein M² is selected from the groupconsisting of scandium, yttrium, and lanthanum; each R⁹ is independentlyhydrogen or C₁-C₅-alkyl; n is 1, 2, 3, 4 or 5; Cp is cyclopentadienylring; and L² is selected from the group consisting of: Cl, F, Br, I, and3,5-R¹⁰R¹¹—C₃HN₂; wherein R¹⁰ and R¹¹ are each independently hydrogen orC₁-C₅-alkyl; wherein when M² is scandium and L² is Cl, R⁹ isC₁-C₅-alkyl.
 26. (canceled)
 27. The metal complex of claim 25, whereineach R⁹ is independently hydrogen or C₁-C₄-alkyl.
 28. (canceled) 29.(canceled)
 30. (canceled)
 31. (canceled)
 32. The metal complex of claim25, wherein M² is scandium, L² is Cl and each R⁹ is independentlymethyl, ethyl or propyl.
 33. (canceled)
 34. (canceled)
 35. The metalcomplex of claim 25, wherein M² is yttrium, L² is 3,5-R¹⁰R¹¹—C₃HN₂ andeach R⁹ is independently methyl, ethyl or propyl.
 36. (canceled)
 37. Themetal complex of claim 25, wherein the complex is: [Sc(MeCp)₂]Cl]₂; and[Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂.
 38. A method of forming a metal-containingfilm by a vapor deposition process, the method comprising vaporizing atleast one metal complex corresponding in structure to Formula I:[(R¹)_(n)Cp]₂M¹L¹   (I) wherein M¹ is selected from the group consistingof scandium, yttrium, and lanthanum; each R¹ is independently hydrogen,C₁-C₅-alkyl or silyl; Cp is cyclopentadienyl ring; and L¹ is selectedfrom the group consisting of: NR²R³; N(SiR⁴R⁵R⁶)₂; 3,5-R⁷R⁸—C₃HN₂;1-(R³²)C₃H₄; 1-R³³-3-R³⁴—C₃H₃; and R³⁵, R³⁶—C₃HO₂; wherein R², R³, R⁴,R⁵, R⁶, R⁷, and R⁸ are each independently hydrogen or C₁-C₅-alkyl; andR³², R³³, R³⁴, R³⁵, and R³⁶ are each independently alkyl or silyl. 39.(canceled)
 40. The method of claim 38, wherein each R¹ is independentlyhydrogen, methyl, ethyl, propyl, or silyl; R², R³, R⁴, R⁵, R⁶, R⁷, andR⁸ are each independently hydrogen, methyl, ethyl or propyl; and R³²,R³³, R³⁴, R³⁵, and R³⁶ are each independently C₁-C₄-alkyl or silyl. 41.The method of claim 38, wherein each R¹ is independently hydrogen,methyl, or ethyl; and R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ are each independentlyhydrogen, methyl, or ethyl; and R³², R³³, R³⁴, R³⁵, and R³⁶ are eachindependently methyl, ethyl, propyl or silyl.
 42. The method of claim38, wherein each R¹ is methyl; R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are eachindependently hydrogen or methyl; and R³², R³³, R³⁴, R³⁵, and R³⁶ areeach SiMe₃. 43-56. (canceled)
 57. The method of claim 38, wherein eachR¹ is independently hydrogen, C₁-C₄-alkyl or silyl; and L¹ is1-(SiMe₃)C₃H₄ or L¹ is 1,3-bis-(SiMe₃)₂C₃H₃.
 58. (canceled) 59.(canceled)
 60. (canceled)
 61. The method of claim 38, wherein thecomplex is: Sc(MeCp)₂[1-(SiMe₃)C₃H₄]; Sc(MeCp)₂[1,3-bis-(SiMe₃)₂C₃H₃];Sc(MeCp)₂[N(SiMe₃)₂]; and Sc(MeCp)₂(3,5-Me₂-C₃HN₂).
 62. The method ofclaim 38, wherein the vapor deposition process is chemical vapordeposition or atomic layer deposition, wherein the chemical vapordeposition is pulsed chemical vapor deposition, continuous flow chemicalvapor deposition, or liquid injection chemical vapor deposition, andwherein the atomic layer deposition is liquid injection atomic layerdeposition or plasma-enhanced atomic layer deposition.
 63. (canceled)64. (canceled)
 65. (canceled)
 66. (canceled)
 67. The method of claim 38,wherein the metal complex is delivered to a substrate in pulsesalternating with pulses of an oxygen source, wherein the oxygen sourceis selected from the group consisting of H₂O, H₂O₂, O₂, ozone, air,i-PrOH, t-BuOH, and N₂O.
 68. (canceled)
 69. The method of claim 38,further comprising vaporizing at least one co-reactant selected from thegroup consisting of hydrogen, hydrogen plasma, oxygen, air, water,ammonia, a hydrazine, a borane, a silane, ozone, and a combination ofany two or more thereof, wherein the hydrazine is hydrazine (N₂H₄) orN,N-dimethylhydrazine.
 70. (canceled)
 71. (canceled)
 72. (canceled)